Photographic silver halide compositions comprising thiourazole adducts

ABSTRACT

This invention relates to photographic compositions comprising adducts of thiourazoles, including dithiourazoles, with unsaturated compounds. Typical useful adducts are made with unsaturated acids, aldehydes, amides, ketones and esters and include monoadducts and diadducts of the thiourazoles.

United States Patent [72] Inventors [54] PHOTOGRAPHIC SILVER HALIDECOMPOSITIONS COMPRISING THIOURAZOLE ADDUCTS 19 Claims, No Drawings [52]U.S. Cl 96/109, 96/66.5, 96/107 [51] Int. Cl G030 l/28, G03c1/34, G03c5/30 [50] Field of Search 96/107,

4 {56T WW References ited UNITED STATES PATENTS 3,148,987 9/l964Williams 96/107 3,433,640 3/1969 Nishio et al.... 96/107 3,447,9276/1969 Bacon et al. 96/107 Primary ExaminerNorman G. Torchin AssistantExaminer-Richard E. Fichter Attorneys-W. H. J. Kline, B. D. Wiese andGerald E. Battist ABSTRACT: This invention relates to photographiccompositions comprising adducts of thiourazoles, includingdithiourazoles, with aB-unsaturated compounds. Typical useful adductsare made with aB-unsaturated acids, aldehydes, amides, ketones andesters and include monoadducts and diadducts of the thiourazoles.

PHOTOGRAPI-IIC SILVER IIALIDE COMPOSITIONS COMPRISING THIOURAZOLEADDUCTS This invention relates to new photographic compositions. In oneaspect, this invention relates to photographic compositions comprisingan adduct of an a, B-unsaturated compound with a thiourazole. In anotheraspect, this invention relates to new silver halide photographiccompositions having reduced minimum density in image areas upondevelopment and after aging and development. In still another aspect,this invention relates to heat-stabilized printout silver halideemulsions having reduced minimum density and better stability.

It is known in the art that urazole compounds and dithiourazolecompounds such as l-phenyl-3,S-dithiourazole are known in the art asantiplumming agents and/or antifogging agents. It is also known thatdithiourazoles may be used in internal image emulsions of the typedescribed in Bacon et al. U.S. Pat. No. 3,447,927, issued June 3, 1969.However, improved internal image emulsions are desired which promotebetter maximum density and lower minimum density with minimum changewhen subjected to prolonged exposures of light. It would also bedesirable to obtain rapid printout in emulsions with the aboveproperties. Moreover, when photographic emulsions are chemicallydeveloped, it would be desirable to obtain improved antifoggantcharacteristics in the emulsion.

We have now found that image properties of photographic emulsions can begenerally improved by utilizing an adduct of an a, B-unsaturated organiccompound with a thiourazole. In one aspect of this invention, theemulsions contain adducts of a, B-unsaturated acids, amides, ketonesaldehydes and esters with thiourazoles (including dithiourazoles). Inanother aspect of this invention, a diadduct is used in the emulsionwhich comprises 2 moles of the a, B-unsaturated compound reacted witheach mole of dithiourazole. Photographic emulsions, particularly silverhalide emulsions, containing the above adducts of thiourazoles exhibitunexpected improvements in photographic properties, stability,low-background fog, increased image density and the like.

In one preferred embodiment, the photographic emulsions comprise athiourazole which is reacted with an a, fl-unsaturated organic aldehydeor ketone.

In another preferred embodiment, the photographic emulsions comprise athiourazole which is reacted with an a, fi-unsaturated acid, ester oramide.

In another embodiment, the photographic emulsions comprise dithiourazoleadducts which have been further reacted with organic compounds such ashydrazines, hydroxylamine, thiosemicarbazides, semicarbazides and thelike.

In another highly preferred embodiment, the thiourazole adducts anddiadducts are used in heat-stablized printout silver halide compositionswhich preferably contain silver halide grains having trivalent metalions, such as bismuth ions, occluded therein.

In another embodiment, we have found that the thiourazole adducts arepreferably dissolved in an alkaline solution before addition to thephotographic emulsion, especially when the thiourazole adducts are addedto printout emulsions which can be heat-stabilized. Generally thethiourazole adducts of this embodiment can be dissolved in basicsolutions containing alkali metal hydroxides, alkali metal carbonates ororganic amines before adding them to the emulsion. Moreover, thethiourazole or dithiourazole can be mixed with the a, B-unsaturatedaldehyde or ketone in an alkali medium, held for at least about one-halfhour and then added to the emulsion to provide improved properties suchas increased photographic speed.

Generally, the thiourazole adducts of this invention are make by thereaction of an a, B-unsaturated compound with a thiourazole of thefollowing formula a tautomer thereof:

wherein X is an oxygen atom, sulfur atom or imino group and R is ahydrogen atom or an alkyl group having form ONE-eight carbon atoms suchas methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like, or anaryl group such as a phenyl group and the like. The a, fi-unsaturate'dorganic compounds preferably have the formula:

R R O N NH l Il -CH wherein X is an oxygen atom, sulfur atom, or iminogroup, and R and R are as represented above and R can be a hydrogen atomor an alkyl group containing from one-l0 carbon atoms.

In another embodiment, photographic compositions of this inventioncomprise the reaction product of an a, ,B-unsaturated acid, ester,ketone or amide with a thiourazole which is believed to be as follows ora tautomer thereof:

wherein R,R R R and'X are as described above. Where a dithiourazole withan Rrepresented by a hydrogen atom is reacted with the a, ,B-unsaturatedaldehyde or ketone, it is believed that a bicyclic compound is formedwhen 2 molar equivalents of the a, B-unsaturated compound are used. Thereaction product is believed to be as follows:

wherein R" R R" R andR are as described above and R is an hydroxylgroup, an amine group, an alkyl ether group, an alkyl group having fromone-I0 carbon atoms. It is understood that R R*- R and R can each bedifferent groups from the other.

In still another embodiment, the photographic compositions comprise theadducts and diadducts of thiourazoles and dithiourazoles which arefurther reacted through the remaining functional reactive groups withorganic compounds such as hydrazines, oximes, semicarbazides,thiosemicarbazides and the like.

The photographic compositions of this invention intended for chemicaldevelopment generally contain the thiourazole adducts in concentrationsof about 0.01 mg. to about 20 g. per mole of the light-sensitivecompound, and preferably from about 0.1 mg. to about g.

In one preferred embodiment, silver halide emulsions according to thisinvention contain antifoggant concentrations of the thiourazole adduct.Where the thiourazole adduct is used in antifoggant concentrations, thepreferred thiourazole adducts comprise an alkyl-carbonyl group.

In one preferred embodiment according to this invention, the thiourazoleadducts have been found to be especially use ful in silver halideemulsions which comprise silver halide grains having polyvalent metalions occluded therein, especially where trivalent metal ions such asbismuth and iridium are occluded in the grains. Typical emulsions ofthis type are disclosed in Bacon et al. U.S. Pat. No. 3,447,927, issuedJune 3, 1969. Silver halide emulsions of this type can be exposed,heat-processed and photodeveloped by various procedures, such as, forexample, by the procedure of Colt, U.S. Pat. No. 3,418,122 issued Dec.24, 1968. In this embodiment, the thiourazole adducts are generallyutilized in the silver halide emulsion in concentrations of up to about100 mole percent, and preferably from about 1 mole percent to about 25percent based on the silver.

The silver halide emulsion of a photographic element according to thisinvention can contain conventional addenda such as gelatin plasticizers,coating aids, antifoggants such as the azaindines and hardeners such asaldehyde hardeners, e.g., formaldehyde, mucochloric acid, glutaraldehydebis (sodium bisulfite), maleic dialdehyde aziridines, vinyl sulfonylethers, dioxane derivatives and oxypolysaccharides and the like.Sensitizing dyes useful in sensitizing such emulsions are described, forexample, in U.S. Pat. No. 2,526,632 of Brooker and white issued Oct. 24,1950, and US. Pat. No. 2,503,776 of Sprague issued Apr. 11, 1950.Spectral sensitizers which can be used are the cyanines, merocyanines,complex (trinuclear) cyanines, complex (trinuclear) merocyanines,styryls and hemicyanines. Developing agents can also be incorporatedinto the silver halide emulsion if desired or can be contained in aseparate underlayer. V arious silver salts can be used as the sensitivesalt such as silver bromide, silver iodide, silver chloride or mixedsilver halides such as silver chlorobromide or silver bromoiodide. Thesilver halides used can be those which form latent images predominantlyon the surface of the silver halide grains or those which form latentimages inside the silver halide crystals such as described in U.S. Pat.No. 2,592,250 of Davey and Knott issued Apr. 8, 1952.

The silver halide emulsion layer of a photographic element which isuseful in the instant invention can contain any of the hydrophilicwater-permeable binding materials suitable for this purpose. Suitablematerials include gelatin, colloidal albumin, polyvinyl compounds,cellulose derivatives, acrylamide polymers, etc. Mixtures of thesebinding agents can also be used. The binding agents for the emulsionlayer of the photographic element can also contain dispersed polymerizedvinyl compoundsv Such compounds are disclosed, for example, in U.S. Pat.Nos. 3,142,568 of Nottorf issued July 28, 1964; 3,193,386 of Whiteissued July 6, 1965; 3,062,674 of Houck, Smith and Yudelson issued Nov.6, 1962; and 3,220,844 of l-louck, Smith and Yudelson issued Nov. 30,1965; and include the water-insoluble polymers and latex copolymers ofalkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates ormethacrylates and the like.

The silver halide emulsion of a'photographic element which is useful inthe instant invention can be coated on a wide variety of supports.Typical supports are cellulose nitrate film,

cellulose ester film, polyvinyl acetal film, polystyrene film,poly(ethylene terephthalate) film, polycarbonate film and related filmsor resinous materials as well as glass, paper, metal and the like.Supports such as paper which are coated with aolefin polymers,particularly polymers of a-olefins containing two or more carbon atoms,as exemplified by polyethylene, polypropylene, ethylenebutene copolymersand the like can also be employed.

The speed of the photographic emulsions useful in the instant inventioncan be further increased by including in the emulsions a variety ofhydrophilic colloids such as carboxymethyl protein of the type describedin U.S. Pat. Nos. 3,011,890 of Gates, .lr., Miller and Koller issuedDec. 5, 1961, and polysaccharides of the type described in Canadian Pat.No. 635,206 of Keller and Russell issued Jan. 23, 1962.

Photographic emulsions useful in the instant invention can also containspeed-increasing compounds such as quaternary ammonium compounds,polyethylene glycols or thioethers. Frequently, useful effects can beobtained by adding the aforementioned speed-increasing compounds to thephotographic developer solutions instead of, or in addition to, thephotographic emulsions.

The photographic elements prepared according to the instant inventioncan be used in various kinds of photographic systems. In addition tobeing useful in X-ray and other nonoptically sensitized systems, theycan also be used in orthochromatic, panchromatic and infrared sensitivesystems. The sensitizing addenda can be added to photographic systemsbefore or after any sensitizing dyes which are used.

The invention can be used in emulsions intended for color photography,for example, emulsions containing color-forming couplers or emulsions tobe developed by solutions containing couplers or other color-generatingmaterials, emulsions of the mixed-packet type such as described in U.S.Pat. No. 2,698,794 of Godowsky issued Jan. 4, 1955; in silver dyebleachsystems; and emulsions of the mixed-grain type such as described in U.S.Pat. No. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.

Silver halide emulsions useful in the instant invention can besensitized using any of the well-known techniques in emulsion making,for example, by digesting with naturally active gelatin or varioussulfur, selenium, tellurium compounds and/or gold compounds. Theemulsions can also be sensitized with salts of noble metals of GroupVIII of the Periodic Table which have an atomic weight greater than 100.

Silver halide emulsions containing the antifoggant of the invention canbe used in diffusion transfer processes which utilize the undevelopedsilver halide in nonimage areas of the negative to form a positive bydissolving the undeveloped silver halide and precipitating it on asilver layer in close proximity to the original silver halide emulsionlayer. Such processes are described in U.S. Pat. Nos. 2,352,014 of Rottissued June 20, 1944: 2,543,181 of Land issued Feb. 27, 1951; and3,020,155 of Yackel, Yutz y, Foster and Rasch issued Feb. 6, 1962. Theemulsions can also be used in diffusion transfer color processes whichutilize a diffusion transfer of an imagewise distribution of developer,coupler or dye from a light-sensitive layer to a second layer while thetwo layers are in close proximity to one another.

While it is preferred to utilize the antifoggants of the invention byincorporating them directly into a photographic element, theantifoggants could also be utilized by incorporating them into aphotographic develop'er, since image formation would still take place inthe presence of the antifoggants and they would still perform theirantifoggant function.

The antifogging agents of this invention can be incorporated toadvantage during manufacture in silver halide emulsions representing thevariations described above. Moreover, fog control in binderless silverhalide films prepared by vapor deposition of silver halide on a suitablesupport can be achieved by coating the antifogging agents of theinvention over the vapor-deposited layer of silver halide. The inventioncan be further illustrated by the following examples of preferredembodiments thereof, although it will be understood that the examplesare included merely for purposes of illustration and are not intended tolimit the scope of the invention unless otherwise indicated.

EXAMPLE 1 3-[s-carboxyethy1thio]-l ,2,4-triazo1ine-5-thione To astirring suspension of 6.65 gms. of 1,2,4-triazolidine- 3,5-dithione in50 ml. of water is added 3.6 gms. of acrylic acid. Within minutes atroom temperature the solids dissolve, and after one-half hour ofstirring a precipitate forms. Stirring continues for an additionalone-half hour and then after chilling the suspension, the precipitate iscollected. The crude product (11 grams) is then recrystallized fromdilute alcohol to produce a yield of 84 percent, m.p. 204205 C.

EXAMPLE 2 EXAMPLE 4 3-[s-N,N-dimethylcarboxamidoethylthio]-4-pheny1-l,2,4- triazoline-5thione This compound is prepared in a manner similarto that described in example 1, except that 1,2,4,-triazolidine-3,5,-dithione is replaced with 1,2,4-triazolidine-4-phenyl-3,5- dithione andacrylic acid is replaced with N,N-dimethylacry1amide to produce a yieldof 82 percent, m.p. l69-7lL C.

EXAMPLE 5 3-[.r-N,N-dimethylcarboxamidoethylthio]- l ,2,4-triazo1ine-S-thione This compound is prepared in a manner similar'to that describedin example 1,except that acrylic-acid is replaced withN.N-dimethylacrylamide to produce a yield of 94 percent, m.p. 90-2L C.

EXAMPLE 6 3-[s-carbobutoxyethylthio] l,2,4-triazoline-5-thione Thiscompound is prepared in a manner similar to that described in example 1,except that acrylic acid is replaced with butylacrylate to produce ayield of 78 percent, m.p. 110-112C.

EXAMPLE 7 3-[s-carboxamidoethylthiol-1,2,4-triazo1ine-5-thione Thiscompound is prepared in a manner similar to that described in example 1,except that acrylic acid is replaced with acrylamide to produce a yieldof 82 percent, m.p. 208-21OBQ C.

EXAMPLE 8 3 [s-methyl-B-carboxamidoethy1thio]-1,2,4-triazo1ine-5- thioneThis compound is prepared in a manner similar to that described inexample 1, except that acrylic acid is replaced with ethylacrylate toproduce a yield of 73 percent, mp. 102-104C.

EXAMPLE l0 l-pheny1-3 ,S-dithiourazole The preparation of this prior artcompound is described in Berichte der Deutscher Chemischer Gesellschaft,1904, Vol. 1, page 184 37th year).

EXAMPLE 1 1 Samples of the compounds of examples l-l0 are added toseparate portions of a high-speed silver bromoiodide emulsion that ispanchromatically sensitized with a cyanine dye. Each emulsion sample iscoated on a cellulose acetate film support at a coverage of 459 mg. ofsilver and 1040 mg. of gelatin per square foot. A sample of each filmcoating is then exposed on an Eastman 1B sensitometer, processed for 5minutes in Kodak DK-SO developer, fixed, washed and dried with thefollowing photographic results.

2 wk. Inc., 120 F.

Rel.

Fog speed v Fog 15 34 96 .66 11 43 98 13 .09 36 .80 10 12 69 1. 20 22 135b 1. 10 l7 11 47 l. 10 15 .12 48 1. 08 20 11 34 .87 .15 10 49 1. 20 1612 44 1. 12 14) 14 (S0 1. 13 28 It can be readily been from the abovetable that the adducts of thiourazoles according to this invention,examples 1-9, exhibit better results as antifoggants in a photographicemulsion than similar previously known compounds such as l phenyldithiourazole, illustrated in example 10.

EXAMPLE 12 3[s-carboxyethylthio]-1,2 ,4-triazoline-5-one one Thiscompound is prepared in a manner similar to that described in example 1,except that 1,2,4-triazolidine-3,5,- dithione is replaced withl,2,4-triazolidine-3-thione-5-one to produce a yield of percent withm.p. of 188-89" C.

-thione-5- EXAMPLE 13 A sample of a compound prepared by the procedureof example 12 is added to a high-speed silver bromoiodide emulsion thatis panchromatically sensitized, coated on a cellulose acetate filmsupport, and exposed and processed as described in example 1 1. Theresults are compared with a control sample which does not contain thecompound prepared according to example 12.

2 Wk. lnc.

Fresh 120 F. 50% RH Adduct of Example No. Rcl. Rel. (p/mol) Speed y1'01: Speed 7 Fog Control 100 1.66 .15 32 .9] .77 12 (3.0) 82 1.67 .1160 1.02 .10

The monothiourazole adduct demonstrates improved sta- I bilization andantifoggant results.

EXAMPLE 14 To a stirred suspension of 53.2 g. (0.4 mole of dithiourazolein 400 ml. of 1:1 alcohol-water at R.T. is added 28 g. (0.4 mole) ofcrotonaldehyde. The suspension warms up as stirring continues and afterapproximately 15 minutes a clear solution results. At the point it isadvisable to warm the solution to 60-70 C. and filter if necessary.Stirring is continued for 1 hour and then the solution is chilled andthe precipitate collected and washed twice with 50 cc. of acid 1:1alcohol-water on the funnel. After drying at 75 C. in a vacuum oven, theyield of the first crop is 47-49 g., m.p. 1902 C.

The combined filtrates yield a second crop of 12-13 g. m.p. 189-19lC.after concentration to approximately two-thirds of the original volume,chilling and seeding with a crystal of the first crop material. Totalyield is 59-62 g. (73-77 percent).

The product may be recrystallized from 50 percent alcohol in 901 15percent yield to give material with m.p. 191-2 C.

EXAMPLE 15 3-(B-acetylethylthio)-1,2,4-triazoline-5-thione is made byadding 6.7 g. of dithiourazole to 3.5 g. of methyl vinyl ketone in 50cc. of 50 percent aqueous. ethyl alcohol. An immediate reaction occurswhich is allowed to proceed with stirring for 1 hour at roomtemperature. The mixture is allowed to settle and is filtered with ayield of g. It is then crystallized out of ethyl alcohol and dried witha yield of 8.5 g., m.p. l46.8 C. Upon recrystallization it yields anm.p. of 152.4 C.

Analysis:

Calculated-C, 35.5; H, 4.4; N, 20.7; S, 31.5

FoundC, 35.8; H, 4.2; N, 20.7; S, 31.2

EXAMPLE 16 A radiation-sensitive gelatin silver bromoiodide photographicemulsion is prepared as described in example 19 of US. Pat. No.3,447,927, issued June 3, 1969. To portions of the emulsion, the halogenacceptors and aldehydes listed below are added. The emulsion samples arecoated on a paper support at about 70 mg. Ag/ft".

Sample lcontaining dithiourazole hydrazine salt at 20 grams per mole andformaldehyde at grams per mole Sample 2containing dithiourazole at gramsand crotonaldehyde at 20 grams per mole Sample3dithiourazole-crotonaldehyde monoadduct of example 14 Samples of eachcoating are then exposed imagewise through a continuous density wedgefor 1 second with a 500- watt lamp and then are heated on an aluminumblock for 5 seconds at a block temperature of 235 C. The samples arethen photodeveloped for 5 minutes at 12 cm. from two 8-watt ultravioletlamps.

Separate sets of these processed coatings are then given the followingexposures to fluorescent room lights: none (control); 24 hours; 7 days;14 days. The following results are obtained:

acrolein is stirred for one-half hour at room temperature. The solidsdissolve within one-half hour with evolution of heat and a precipitateforms on cooling. The material is collected and crystallized out ofethanol to yield 5.3 g. of product m.p. 1246 C. This material isidentical by melting point, mixture melting point and IR spectra withthat obtained by method A.

EXAMPLE 18 A suspension of 11.7 g. of monothiourazole and 5.6 g. ofacrolein in ml. of 50 percent ethanol is stirred at room temperature.After 1 hour, the solids dissolve; stirring is continued for 2 hours. Atthe end of this time the solution is chilled to yield 15 g. of product.Recrystallization from 50 percent ethanol yields 10 g. of material withm.p. 209-2l0 C.

Foundz-N, 24.5

EXAMPLE 19 A solution of 3.0 g. of monothiourazole and 1.8 g. ofcrotonaldehyde in 20 ml. of 50 percent ethanol is stirred 2 hours atroom temperature and then chilled. The precipitate (3.3 g.) iscrystallized out of ethanol to yield product m.p. 217-8 C.

Calcd. for C H N 0,S:C, 38.7; H, 4.8; N, 24.8; S, 16.1

Foundz-C, 38.3; 1-1, 5.2; N, 24.5; S, 16.5

EXAMPLE 20 When dithiourazole is allowed to react with 2 moles of methylvinyl ketone in water, well cooled with ice, an almost quantitativeyield of the monoadduct precipitates within a short time. Thisprecipitate (m.p. 152-4" C.), when allowed to react in water for anadditional 18 hours at room temperature with stirring, graduallydissolves to form a new compound, the diadduct (m.p. 82-4 C.)precipitated in high yields on coolmg.

EXAMPLE 21 A radiation-sensitive gelatin silver bromoiodide photographicemulsion is prepared as described in example 19 of US. Pat. No.3,447,927, issued June 3, 1969. To portions of the emulsion, thedithiourazole adductslisted below and a spectral-sensitizing dye at aconcentration of 150 g./Ag mole are added. The emulsion samples arecoated on a paper support at about 70 mg. Ag/ft". Samples of eachcoating are then exposed, heated at 250 C. for 5 minutes on a Teflonsurface and photodeveloped with the following results.

Heatstabi1ized at 235 C.exposure to fluorescent light Control 24 hours 7days 14 days Addenda Dmlx, Dmin, Drnnz, Dmin. Dmnx. Drain. mnx. min.

Sample EXAMPLE 17 Method A: A suspension of 9.5 g. of adduct of example15 Phomgrapmc Rcsuhs and 3.5 g. of acrolein in 100 ml. of 50 percentethanol is Adduct(g./mole of Ag) m D..,.,, stirred at room temperaturefor 18 hours. The solids dissolve after one-half hour and a precipitatebegins to appear after 6 A (15) 16 hours. The suspension is chilled andthe collected precipitate B 12 is recrystallized out of ethanol to yield10.2 g. of product m.p. 70 g 8 o 126-7 E (is) 1.12 .08 Calcd. for C H, NO S,:N, 16.2 F 34) 1.04 .07 Found: N 16.5 G (34) 1.16 .04 Method B: Asuspension of 5.1 g. of monoadduct of exami2 '5; 1 1. .04

ple 15in 46 ml. of water-ethanol (2:1) containing 1.5 g. of

EXAMPLE 22 The thiourazole adducts are preferably dissolved in a 11alkaline medium before addition to silver halide emulsions. Aradiation-sensitive gelatin silver bromoiodide photographic emulsion isprepared as described in example 19 of US. Pat. No. 3,447,927, issuedJune 3, 1969. Thiourazole adducts are added to the emulsion at 20 gramsper mole along with the spectral-sensitizing dye 3-ethyl-5-[(3ethyl-2-benzothiazolinylidene)-lmethylidene]-2thio-2,4-oxazolidinedioneat a concentration of 150 milligrams per mole of silver. The emulsion iscoated and after exposure is heated on an aluminum block for seconds ata temperature of 235 C. and then photodeveloped. The thiourazole adductsare added under the following conditions:

Sample 1 An adduct prepared according to example 14 is dissolved inmethanol and added to the emulsion which is coated at a pH of5.0.

Sample 2 An adduct prepared according to example 14 is dissolved inmethanol and added to the emulsion which is then adjusted to a coatingpH of 6.5 with sodium hydroxide.

Sample 3 An adduct prepared according to example 14 is dissolved inwater and the pH adjusted to 1 1.4 with sodium hydroxide before addingit to the emulsion which is coated at a pH of 6.5.

Sample 4 Dithiourazole and crotonaldehyde are mixed in equal weightportions in water and adjusted to a pH of 1 1.4 with sodium hydroxideand held for about one-half hour before adding it to the emulsion at aconcentration of 40 grams per mole of silver which is then coated at apH of 6.5.

Sample 5 An adduct prepared according to example 15 is dissolved inwater and the pH adjusted to 1 1.4 with sodium hydroxide and held forabout 1 hour. The above adduct (or equilibrium product) is added to theemulsion at a concentration of 25 grams per mole of silver and is thencoated at a pH of 6.5.

Photographic Results Sample D,,,,, y Rel. Speed and acrylic acid withmonothiourazole are substituted in the preparation of example 5.Moreover, similar improvements LII are obtained when the alkalinesolutions above are dried down and the solids are redissolved in waterbefore addition to the emulsion.

EXAMPLE 23 Analysis for C H ON S Calcd.:-N, 25.7 Found:-N, 25.7

EXAMPLE 24 10.15 g. of the adduct prepared according to example 15 aredissolved in 50 cc. of 50 percent aqueous ethyl alcohol. 5.25 g. of4-methy1-3-thiosemicarbazide in 50 cc. of 50 percent aqueous ethylalcohol are added. After reaction, the product is settled, chilled andfiltered with a yield of 15 g. at m.p. of 187-189 C.

Analysis for C H N S Calcd.:-N, 29.0 Found: N, 28.6

EXAMPLE 25 10.1 g. of the adduct prepared according to example 15 aredissolved in 100 cc. of 50 percent ethyl alcohol and reacted with phenylhydrazine at boiling temperature for one-fourth delete hour. Theprecipitate yields 8 g. of product with m.p. of 155 C.

Analysis for C H, N S Calcd.: N, 23.9 Found: N, 23.7

EXAMPLE 26 2 Wk. 1110., 120 F./50%

Fresh Compound Relative Relative (gjmole) speed 7 Fog speed 1 Fog C100 1. 41 .16 35. 5 99 72 A. 82 1. 17 .11 71 1.18 29 B. 71 1. 27 10 621.17 .34 C. 85 1. 38 11 74 1. 30 15 D. 91 1. 72 .11 59 1.15 .17 E. 1181.55 .10 62 1. 20 .27 F. 120 1. 68 10 67 1. 30 .18 G. 102 1. 45 .15 24.83 26 H. 1. 48 12 52 1.00 25 I. 91 1. 43 .11 73 1. 03 15 J. 74 1. 40.14 71 1. 25 .22 K. 71 1. 25 .12 80 1. 22 .19 L. 53 1.10 .14 33 .88 7 M.60 1. 43 .13 52 1.13 5

of 3-[d-ketobutylthio]- l ,2,4-

l-l-6,7-dihydro--hydroxy-3 ('y-ketobutylthio )-7 -methyl-[5l-l]-s-triazolo[3 ,4-b][ 1,3 l-thiazine I- 3 -(B-acetylethylthio)-6,7-dihydro-5 -hydroxy-6- methyl[5-l-l ]-s-triazolo[3 ,4-b][ 1,3]-thiazine J 3-carbethoxyethylthio-6,7-dihydro-5-hydroxy-S -methyl-[5-l-l]-s-triazolo[3,4-b][1,3]-thiazine K- 3-( carbethoxyethylthio)-6,7-dihydro-5-hydroxy-[ 5H s-triazolo-[ 3 ,4-b] ,3 ]-thiazine L-3-(7-ketobutylthio )-5 -oxol ,2 ,4-triazolidine M3-(a-methyl-fi-carbethoxyethylthio l ,2,4-triazoline-5- thione EXAMPLE27 The thiourazole adducts are advantageously used in color photographicsystems as antifoggants.

The thiourazole derivatives listed in the following table are added toseparate portions of a red-sensitive sulfur and goldsensitizedgelatin-silver bromoiodide emulsion containing a dispersion of acyan-forming phenolic coupler of the type described in U.S. Pat. No.2,474,293 as Compound 1. The emulsion samples and a control are coatedon a cellulose acetate film support at 100 mg. Ag/ftf" and 272 mg.gelatin/ft A sample of each film coating is exposed on an Eastman 1Bsensitometer and processed in the Eastman Color Negative Process C-22(12 development). The results in the following table illustrate theantifoggant and stabilization advantage obtained from the use ofthiourazole adducts.

Fresh 1 wk. incubation Compound Rel. Rel. (g./Ag mole) speed 7 Fog speed7 Fog EXAMPLE 28 Vinyl sulfonyl ethers are preferably used as hardenersin combination with the thiourazole adducts in photographic emulsionscontaining hydrophilic colloids such as gelatin. A radiation-sensitivegelatino-bromoiodide (6 mole percent iodide) emulsion precipitated inthe presence of bismuth ions according to Bacon et al. U.S. Pat. No.3,447,927 is coated on a paper support at 60 mg. Ag/ft. and 550 mg.gelatin/ft To the emulsion is added bis(vinyl sulfonylmethy1)ether at2.4 g./silver mole and an alkaline solution (pH 1 1.2) of 3-lthiapentan-4one)-l,2,4-triazoline-5-thione at 34 g./silver mole. Thehardened coating is then processed by the following steps.

1. exposing one-tenth second on an Eastman 1B sensitometer through a 0.l 5 FD step wedge;

2. heating at 235 C. for 4 seconds on a hot platen; and

3. photodeveloping 5 minutes at 6 inches from a No. 2

reflector photoflood lamp.

The processed coating exhibits 16 steps with a maximum density of 1.27and a minimum density of 0.09.

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations, and modifications can be effected within the spirit andscope of the invention.

We claim:

1. A photographic composition comprising a silver halide emulsion and anantifoggant concentration of an adduct of a thiourazole compound of thefollowing formula or a tautomer thereof:

wherein X can be an oxygen atom, sulfur atom, or an imino group, and Ris a hydrogen atom, an alkyl group having from one to eight carbonatoms, or a phenyl group; with an a, B-unsaturated organic compoundhaving the formula:

wherein R and R can be a hydrogen atom or an alkyl group containing fromone to four carbon atoms, and R can be a hydrogen atom, a hydroxylgroup, an amine group, an alkyl ether group having from one to 10 carbonatoms, or an alkyl group having from one to 10 carbon atoms.

' 2. A photographic composition according to claim 1 wherein said a,B-unsaturated organic compound is an aldehyde or ketone.

3. A photographic composition according to claim 1 wherein said a,B-unsaturated organic compound is an acid, ester, or amine.

4. A photographic composition according to claim 1 wherein X is a sulfuratom.

5. A photographic composition according to claim 1 wherein said adductis a diadduct wherein X is a sulfur atom and R is a hydrogen atom.

6. A photographic composition according to claim I wherein said a,B-unsaturated compound is crotonaldehyde.

7. A photographic composition according to claim 1 wherein said a,B-unsaturated compound is methyl vinyl ketone.

8. A photographic composition according to claim 1 wherein said adductis a diadduct of dithiourazole with crotonaldehyde, methyl vinyl ketone,or a mixture thereof.

9.. A composition according to claim 1 wherein said adduct is3(B-acetylethylthio-l ,2,4-triazoline-5-thione.

10. A composition according to claim 1 wherein said adduct is 3[-acetylethylthio l ,2,4-triazoline-5 -thione.acetylethylthio]-6,7-dihydro-5-hydroxy-5-methyl-5H-striazolo[3,4-b l ,3]-thiazine.

11. A photographic composition according to claim 1 which furthercomprises a hydrophilic colloid and a vinyl sulfonyl ether hardener.

12. A process for preparing a photographic composition as set forth inclaim 1 which comprises dissolving said adduct in an alkaline medium andthen adding it to the silver halide emulsion.

13. A process for preparing a photographic composition as set forth inclaim 1 which comprises mixing the thiourazole with the a, B-unsaturatedcompound in an alkali medium so as to obtain an adduct and then addingit to a photographic emulslon.

14. A photographic composition according to claim 1 wherein said adductis present in a concentration of from about 0.01 mg. to about 20 gramsper mole of silver.

15. A photographic composition according to claim 1 wherein said adductis present in a concentration of from about 0.1 mg. to about 10 gramsper mole of silver.

16. A light-developable direct-print photographic composition comprisinga silver halide emulsion in which the silver halide grains havetrivalent metal ions occluded therein, and from about 1 to mole percent,based on the silver, of an adduct of a thiourazole compound of thefollowing formula or a tautomer thereof:

HNN

X=C C-SH wherein X can be an oxygen atom, sulfur atom, or an iminogroup, and R is a hydrogen atom, an alkyl group having from one to eightcarbon atoms, or a phenyl group; with an a, B-unsaturated organiccompound having the formula:

wherein R and R 2 can be a hydrogen atom or an alkyl group containingfrom one to four carbon atoms, and R can be a hydrogen atom, a hydroxylgroup, an amine group, an alkyl ether group having from one to 10 carbonatoms, or an alkyl group having from one to 10 carbon atoms. I

17. A composition according to claim 16 wherein said trivalent metalions are bismuth ions, and said adduct is present in a concentration offrom about 1 to about 25 mole percent, based on the silver.

18. A photographic element comprising a support, a silver halide layer,and as an addendum, an antifoggant concentration of an adduct of athiourazole compound of the following formula or a tautomer thereof:

one to eight carbon atoms, or a phenyl group; with an a, B-unsaturatedorganic compound having the formula:

wherein R and R can be a hydrogen atom or an alkyl group containing fromone to four carbon atoms, and R can be a hydrogen atom, a hydroxylgroup, an amine group, an alkyl ether group having from one to 10 carbonatoms, or an alkyl group having from one to 10 carbon atoms.

19. A photographic element comprising a support, a silver halide layerhaving trivalent metal ions occluded in the silver halide grainsthereof, and from about 1.0 to about 25 mole percent, based on thesilver, of an adduct of a thiourazole compound of the following formulaor a tautomer thereof:

wherein X can be an oxygen atom, sulfur atom, or an imino group, and Ris a hydrogen atom, an alkyl group having from one to eight carbonatoms, or a phenyl group; with an or, B-unsaturated organic compoundhaving the formula:

mutiny wherein R and R can be a hydrogen atom or an alkyl groupcontaining from one to four carbon atoms, and R can be a hydrogen atom,a hydroxyl group, an amine group, an alkyl ether group having from oneto 10 carbon atoms, or an alkyl group having from one to 19 ca rbo n atoms.

mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,615,618 Dated October 97 Inventor) Albert W, Wise, John W. Gates, Jr.Dorothy J. Beavers It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

I' Column 1 line 69, after "formula", please insert--or---."|

Column 2, line 2, "form" should read ---from---. Column 3, line L 1"white" should read --white--; line 8, "V arious" should read--Various---. Column L line I 7, antifo ant" should read---antifoggants---. Column 5, line 8, "3- s-oarboxyethylthig7-1,2,L-triazoline-5-thione" should read ---3- jB- carboxyethylthig7-1 ,2,L-triazoline -5'-thione---; line 27 "triazolidene" should read---triazolidine---; line 33, "3--N,N- dimethylcarboxamidoethylthi27-L-phenyl-1 ,2,L -triazoline-5-thione" should read --3-/-N,N-dimethylcarboxamidoethylthi97L .-phenyl- 1 ,2,triazoline-B'-thione---; line 39, "1 69-71 LC should read ---1 9-71C-----; line L Z, "B-E-DLN-dimethyloarboxamidoethylthi27- 1 ,2,L-triazoline -5-thione" should read --3-[)3-II,I\I-dimethyloarboxamidoethylthipjd ,2,L -triazoline -5-thione---; lineL N.Ndimethylacylamide" should read --I I,I I-dimethy1aoylamide--; lined7, "90-2LC" should read 490-2 0; line 51, "3-5- oarbobutoxyethylthig7-1,2,L -triazoline-5-thione" should read --3-/ }3-carbobutoxyethylthig7-1,2, triazoline-5thione---; line F9, "3-5-carb0x&mid0ethylthi9 -1 ,2,-triazoline-5thione" should read -3-FB-carboxamidoethylthi2 -1 ,2,L-triazoline-5 thione--; line 6?, "208-210B c" should read---208-21oc.---; line 66, "3-/-methyl-B-carboxamidoethylthig7-1 ,2,L-triazoline- 5-thione" should read ---3-/ }3-methyl- -oarboxamidoethlthio7- 1 ,2,L -triazoline 5-thione-:. Column 6, line 1 .0, "3-s-oarhoxyethylthio7-1 ,2,L -triazoline-5-one -thione -S-one" should read--3-[ carboxyethylthio7-1 ,2,L -triazoline-5-one-; line 72, after'mole", please insert Column 7 line 13, "90115" should read ---90 Column9, line 1 "3- soarboxamido-B- methylethylthi9 71,2,h-triazoline-E-thione" should read --3/ }3-carboxamido-fi-methylethylthig7-1 ,2,) -triazoline-5-thione---;

Page 1 of 2 pages J 32 3 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3, 5, 5 Dated October 97 Inventor) Albert w, wise,John W. Gates, Jr. Dorothy J. Beavers It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

' Column 9, line 3, "3-/ -carbobutoxyethylthig7-1,2,L -triazoline5-thione" should read --3/ )3-carbobutoxyethylthig7-1 2,Ltriazoline-5-thione---; line 8, "3- s-carboxyethylthig7- ,2,L triazoline-5-thione" should read ---3-[B-carboxyethylthig7- 1 ,2,L-triazoline-5-thione---; line 11 "3-/-carboxyethylthio7h-hydroxy-6-methyl-1 ,2,3a-triaza7-thia-h, ,6-trihydroindene" shouldread --3-/ }3-oarboxyethylthig7-h-hydroxy-6-methyl- 1 ,2,3atriaza-7-thia-L;.,5',6-trihydroindene---; line 13, "3-5- acetylethylthio7-I-hydroXy-6methyl-1 ,2,3atriaza7-thia-h,,6- trihydroindene" should read-3-/ )3-acetylethylthig7-h-hydroxy- 6-methyl-1,2,3a-triaza-7-thia-h,5":6-trihydroindene---; line 62,

in Sample 2, "0.50" should read ---O.5L Column 10, line 15, "1940-195 0"should read ---19L .5c---; line 27, "187-189 0" should read --1 87.9C---; line 36, before "hour", please delete the word ---delete---; line69, "Phenylhydrazone of B-E-ketobutylthio7-1 ,2,h-triazoline-S-thione"should read ---Phenylhydrozon eT of 3-H -ketobutylthi o7-1,2,h-triazoline-E-thione---. Column 11 line HO, "3-/s-oarboXyethylthio7-1 ,2,L -triazoline-5- thione" should read)3-carboxyethyltEio7-1 ,2,LL-triazoline5- thione---; line Lu, "3/-N,Ndimethylcarboiamidoeth lthio7-l phenyl-1 ,2,L; -triazoline 5-thione"should read -3- 4 g-N,N dimethylcarboxamidoethylthi 7-L -phenyl-1,2,htriazoline-5-thione---; line L B, "3/ s-methyl-}3-oarboxyethylthig7-1 ,2,L .-triazoline -5- thione" should read--3-[}3-methyl-}3carboxyethylthig 71 ,2,L triazoline -5-thione--; line15, "3/ s-methyl-j3-oarbomethoxyethylthi27-1 ,2,L -triazoline -Sthione"should read ---3- )3-methyl- B-oarbomethoXyethylthi27-1 ,2,L -triazoline-S:thione---; line 66, "FD" should read ---AD---. Claim 10, l-aoetylethylthio)- 1 ,2,L,L-triazoline-5thione.acet leth lthi o-6,7-dihydro-5-hydroxy- 5-meth1l-5H-s-triaz0lof ,h-h [1 ,1 -thiazine.should read --3/ )3-aoetylethylthio-6,Y-dihydro-S-hydroxy-S-methyl-EH-striazoloL 3,hQ7L 1 ,i7- hiazine---.

Page 2 of 2 pages Signed and sealed this 1st day of August 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attestlng Officer Commissionerof Patents

2. A photographic composition according to claim 1 wherein said Alpha , Beta -unsaturated organic compound is an aldehyde or ketone.
 3. A photographic composition according to claim 1 wherein said Alpha , Beta -unsaturated organic compound is an acid, ester, or amine.
 4. A photographic composition according to claim 1 wherein X is a sulfur atom.
 5. A photographic composition according to claim 1 wherein said adduct is a diadduct wherein X is a sulfur atom and R is a hydrogen atom.
 6. A photographic composition according to claim 1 wherein said Alpha , Beta -unsaturated compound is crotonaldehyde.
 7. A photographic composition according to claim 1 wherein said Alpha , Beta -unsaturated compound is methyl vinyl ketone.
 8. A photographic composition according to claim 1 wherein said adduct is a diadduct of dithiourazole with crotonaldehyde, methyl vinyl ketone, or a mixture thereof.
 9. A composition according to claim 1 wherein said adduct is 3( Beta -acetylethylthio-1,2,4-triazoline-5-thione.
 10. A composition according to claim 1 wherein said adduct is 3(-acetylethylthio)-1,2,4-triazoline-5-thione. -acetylethylthio)-6,7-dihydro-5-hydroxy-5-methyl-5H-s-triazolo(3,4-b)(1,3) -thiazine.
 11. A photographic composition according to claim 1 which further comprises a hydrophilic colloid and a vinyl sulfonyl ether hardener.
 12. A process for preparing a photographic composition as set forth in claim 1 which comprises dissolving said adduct in an alkaline medium and then adding it to the silver halide emulsion.
 13. A process for preparing a photographic composition as set forth in claim 1 which comprises mixing the thiourazole with the Alpha , Beta -unsaturated compound in an alkali medium so as to obtain an adduct and then adding it to a photographic emulsion.
 14. A photographic composition according to claim 1 wherein said adduct is present in a concentration of from about 0.01 mg. to about 20 grams per mole of silver.
 15. A photographic composition according to claim 1 wherein said adduct is present in a concentration of from about 0.1 mg. to about 10 grams per mole of silver.
 16. A light-developable direct-print photographic composition comprising a silver halide emulsion in which the silver halide grains have trivalent metal ions occluded therein, and from about 1 to 100 mole percent, based on the silver, of an adduct of a thiourazole compound of the following formula or a tautomer thereof:
 17. A composition according to claim 16 wherein said trivalent metal ions are bismuth ions, and said adduct is present in a concentration of from about 1 to about 25 mole percent, based on the silver.
 18. A photographic element comprising a support, a silver halide layer, and as an addendum, an antifoggant concentration of an adduct of a thiourazole compound of the following formula or a tautomer thereof:
 19. A photographic element comprising a support, a silver halide layer having trivalent metal ions occluded in the silver halide grains thereof, and from about 1.0 to about 25 mole percent, based on the silver, of an adduct of a thiourazole compound of the following formula or a tautomer thereof: 